Dynamics Of Anisotropic Gold Nanopartilces In Synthetic And Biopo

Wayne State University Wayne State University Dissertations 8-1-2015 Dynamics Of Anisotropic Gold Nanopartilces In Synthetic And Biopolymer Solutions Sharmine Alam Wayne State University, Follow this and additional works at: http://digitalcommons.wayne.edu/oa_dissertations Part of the Physics Commons Recommended Citation Alam, Sharmine, "Dynamics Of Anisotropic Gold Nanopartilces In Synthetic And Biopolymer Solutions" (2015) Wayne State University Dissertations Paper 1330 This Open Access Dissertation is brought to you for free and open access by DigitalCommons@WayneState It has been accepted for inclusion in Wayne State University Dissertations by an authorized administrator of DigitalCommons@WayneState DYNAMICS OF ANISOTROPIC GOLD NANOPARTICLES IN SYNTHETIC AND BIOPOLYMER SOLUTIONS by SHARMINE ALAM DISSERTATION Submitted to the Graduate School of Wayne State University Detroit, Michigan in partial fulfillment of the requirements for the degree of DOCTOR OF PHILOSHOPY 2015 MAJOR: PHYSICS Approved by: Advisor Date © COPYRIGHT BY SHARMINE ALAM 2015 All Rights Reserved DEDICATION To my parents and my brother, whose support motivated me to continue my academic and professional goals ii ACKNOWLEDGEMENTS It is my great pleasure to have the opportunity to thank the numerous individuals for their support, motivation and encouragement during my academic career First, I would like to express my sincere gratitude towards my advisor Dr Ashis Mukhopadhyay for all his valuable guidance and endless support in my research I surely benefited and learnt a lot from his knowledge in soft condensed matter physics, which has been my primary research focus for past four years His method of research, guidance during my experiments, comments and feedback in preparation of manuscripts as well as during the writing of this thesis have been of critical importance I would also like to thank him for all his valuable advice related not only to my research, but also to matters involving my future career outside Wayne State University I sincerely appreciate him for all his guidance and encouragement I would also like to thank Dr Zhixian Zhou, Dr Takeshi Sakamoto and Dr Vaman Naik to have graciously agreed to be part of my dissertation committee They have taken time out of their busy schedule to ensure my thesis meets the standard for publications by providing their valuable questions, feedback and comments Special thanks must go out to my family for their support and encouragement throughout my all academic pursuits I wish to thank Dr Indermeet Kohli, my senior lab colleague for her help in guiding me with the instruments and materials I also wish to acknowledge my other lab colleagues – Andrew Aneesse, Bhavdeep Patel and Namita Shokeen for their help, assistance and interaction during my research Finally, I would like to thank Dr Ratna Naik for all her valuable advice and guidance during my graduate study and to give me the opportunity to conduct research at Wayne State University I really appreciate her for being so considerate and supportive from the very beginning iii TABLE OF CONTENTS Dedication ii Acknowledgements iii List of Figures vii List of Tables xii Chapter – Introduction 1.1 Soft Matter 1.2 Polymers 1.3 Significance of Research .13 Chapter – Background 16 2.1 Introduction 16 2.1.1 Previous Theoretical Work 16 2.1.2 Computational Studies .23 2.1.3 Previous Experimental Work 24 2.2 Previous Work on Biopolymers .26 2.3 Previous Work on Rod/Sphere Mixtures 29 2.3.1 Theoretical Work .29 2.3.2 Computational Studies .32 2.3.3 Experimental Studies .33 Chapter - Fluorescence Correlation Spectroscopy 35 3.1 Introduction 35 3.2 Experimental set-up for FCS 38 3.3 FCS Theory 42 Chapter - Dynamics of Anisotropic Particles Synthetic Polymer Solutions .45 4.1 Translational and Rotational Diffusions of Nanorods iv within Semidilute and Entangled Polymer Solutions 45 4.2 Experimental Section .47 4.3 Results and Discussion 49 4.4 Conclusions 65 4.5 Supporting Information 66 Chapter - Dynamics of Anisotropic Particles in Biopolymer Solutions 68 5.1 Conjugation of Gold Nanorods with Bovine Serum Albumin Protein 68 5.2 Experimental Section .70 5.3 Results and Discussion 71 5.4 Conclusions 82 5.5 Supporting Information 83 Chapter – Dynamics of Anisotropic Particles in Sphere Mixtures 84 6.1 Translational Anisotropy and Rotational Diffusion of Gold Nanorods in Colloidal Sphere Solutions 84 6.2 Experimental Section .87 6.3 Results and Discussion 90 6.3.1 Translational Diffusion 91 6.3.2 Rotational Diffusion 96 6.4 Conclusions 99 6.5 Supporting Information 100 Chapter – Dynamics of Nanospheres in Biopolymer Solutions 104 7.1 Interaction and Diffusion of Gold Nanoparticles in Bovine Serum Albumin .104 Chapter – Conclusions 111 v References .112 Abstract 122 Autobiographical Statement 124 vi LIST OF FIGURES Figure 1.1.1: (a) colloidal particles, (b) liquid crystal, (c) amphiphiles, (d) polymer Figure 1.2.1: Examples of Polymer architectures: linear, ring, star-branched, H-branched, comb, ladder, dendrimer, and randomelybranched Figure 1.2.2: (a) alternating copolymer, (b) random copolymer, (c) block copolymer, and (d) graft copolymer Figure 1.2.3: Different concentration regimes of flexible polymers 10 Figure 1.2.4: Different concentration regions of polymeric solution 11 Figure 1.3.1: Trafficking of AuNRs in cancer cells (Reprinted with permission from Nano Letters, 2011, 11, 772-780 Copyright (2011) American Chemical Society) 14 Figure 2.1.1: (i) Terminal particles diffusion coefficient Dt as a function of particles size d in entangled polymer solutions (ii) Normalize terminal diffusion as a function of polymer concentration in entangled athermal polymer coefficient solutions (Reprinted with permission from Macromolecules, 2011, 44, 78537863 Copyright (2011) American Chemical Society) 22 Figure 3.1.1: Fluctuation of fluorescence due to molecular dynamics and generation of autocorrelation function (ACF) 36 Figure 3.1.2: Fluctuation of fluorescence due to molecular dynamics and generation of cross-correlation function (CCF) .37 Figure 3.1.3: (a, b): Model autocorrelation curves for different kinds of particle motion: free diffusion in three dimensions (red), free diffusion in two dimensions, e.g., for membrane-bound molecules (yellow) and directed flow (Cyan) 38 Figure 3.2.1: Two photon FCS set up for translational diffusion measurements 39 vii Figure 3.2.2: Diagram of two photon excitation 40 Figure 4.1.1: UV-vis spectra of AuNR in water (open square) with two distinct peaks at 790 nm and 510 nm The peak at 790 nm depends upon the aspect ratio of the rod .46 Figure 4.3.1: Autocorrelation function showing both the rotational and translational diffusion of the nanorods in water collected by using polarized MP-FCS The solid line is fitting with the models described in the text giving DR= 33556  540 s-1 and DT= 14.7  0.3 m2/s The measured DR corresponds to rotation perpendicular to the long axis of the rod and DT is the center-of-mass diffusion of the rod averaged over all orientations (Inset) Transmission Electron Micrograph of gold colloids deposited on carbon film magnified 100 000x A JEOL 2010 TEM with a LaB6 filament working at 200kV was employed to capture the image The length and diameter of 150 such particles are shown, which gave the average L56 nm and d13 nm The corresponding histograms are shown in Fig 4.5.1 50 Figure 4.3.2: Translation (top) and rotation (bottom) diffusion coefficients as a function of polymer volume fraction The data has been normalized with respect to the diffusion coefficients in water The solid lines show fits according to Cuckier model The caption indicates the polymer molecular weight The crossover volume fractions (* and e) are also shown The data indicates that diffusion of nanorods is faster compared to hydrodynamic prediction for higher molecular weights 57 Figure 4.3.3: In log-log plot, the comparison of D() with scaling theory (Ref 1) is shown The scaling predictions are solid line The open symbols are translational diffusion and filled symbols are rotational diffusion The two crossover volume fractions, ξ and d are also shown by the dashed lines All the relevant parameters are listed in Table 4.3.2 The data for 5K was not plotted as they agree with hydrodynamic theory 60 Figure 4.3.4: The nanoviscosity, c () is compared with the bulk viscosity, b () for three different molecular weights as a function of polymer volume fraction,  Both translation and rotation are governed by the same nanoviscosity for the AuNR studied The solid symbols are rotational and open symbols are translational nanoviscosity The solid line is the bulk viscosity In 5K and 35K PEG solutions, c () b (), but deviations were observed in 150K solution 62 viii 111 CHAPTER CONCLUSIONS The experiments comprising in my dissertation have focused on investigating the dynamics of anisotropic gold nanoparticles in polymeric and colloidal systems Understanding the interaction of anisotropic nanoparticles with macromolecules (polymers, proteins, and colloids) has technological as well as biomedical interests such as developing high performance polymeric materials, nano-template surfaces, and effective drug delivery vehicles For the investigations, fluorescence correlation spectroscopy (FCS) was performed, which can offer structural and dynamical information about these systems at shorter length scales These experiments allowed us to report important observations in Chapters – and my collaborative work with Dr Kohli in Chapter Nanoparticles are being widely used as drug carrier and therapeutic agents In many cases, however, the particles have to cross the mucus gel, which can act as a formidable barrier to nanoparticles drug-delivery systems Mucus is a slippery secretion produced from cells found in mucus glands, which act as a lubricant This barrier is important for humans as well as animals as it protects 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136 M Lundqvist, J Stigler, G Elia, I Lynch, T Cedervall and K A Dawson, P Natl A Sci 105 (38), 14265-14270 (2008) 137 X Shi, D Li, J Xie, S Wang, Z Wu and H Chen, Chinese Sci Bull 57 (10), 1109-1115 (2012) 138 M A Dobrovolskaia, A K Patri, J Zheng, J D Clogston, N Ayub, P Aggarwal, B W Neun, J B Hall and S E McNeil, Nanomed Nanotechnol (2), 106-117 (2009) 121 139 P Aggarwal, J B Hall, C B McLeland, M A Dobrovolskaia and S E McNeil, Adv Drug Deliver Rev 61 (6), 428-437 (2009) 140 E Casals, T Pfaller, A Duschl, G J Oostingh and V Puntes, ACS Nano (7), 3623- 3632 (2010) 122 ABSTRACT DYNAMICS OF ANISOTROPIC GOLD NANOPARTICLES IN SYNTHETIC AND BIOPOLYMER SOLUTIONS by SHARMINE ALAM August 2015 Advisor: Dr Ashis Mukhopadhyay Major: Physics Degree: Doctor of Philosophy Soft matter is a subfield of condensed matter physics including systems such as polymers, colloids, amphiphiles and liquid crystals Understanding their interaction and dynamics is essential for many interdisciplinary fields of study as well as important for technological advancements We used gold nanorods (AuNRs) to investigate the length-scale dependent dynamics in semidilute polymer solutions, their conjugation and interaction with a protein bovine serum albumin (BSA), and the effect of shape anisotropy on the dynamics within a crowded solution of spheres Multiphoton fluctuation correlation spectroscopy (MP-FCS) technique was used to investigate the translation and rotational diffusion of AuNRs For polymer solutions, we determined the nanoviscosity experienced by the rods from the measured diffusion coefficient Our results showed the importance of microscopic friction in determing the particle dynamics In BSA solutions, we observed a submonolayer formation at the AuNRs surface, which indicates loss of protein native conformation For rod – sphere mixture, our results 123 indicated significant diffusional anisotropy for translational motion, whereas the rotation of the rods closely followed the ‘caging theory’ 124 AUTOBIOGRAPHICAL STATEMENT SHARMINE ALAM Education:  2010-2015, Wayne State University, Detroit, MI: Ph.D in Condensed Matter Physics  2010-2013, Wayne State University, Detroit, MI: MS in Physics  2003-2008, University of Dhaka, Dhaka, Bangladesh: BS in Physics Publications: Sharmine Alam and Ashis Mukhopadhayay “Translational Anisotropy and Rotational Diffusion of Gold Nanorods in Colloidal Sphere Solutions”, Langmuir, DOI: 10.1021/acs.langmuir.5b01682, (2015) Sharmine Alam and Ashis Mukhopadhyay, “Conjugation of Gold Nanorods with Bovine Serum Albumin Protein”, The Journal of Physical Chemistry C, 118 (47), 27459–27464 (2014) Sharmine Alam and Ashis Mukhopadhyay, “Translational and Rotational Diffusions of Nanorods within Semidilute and Entangled Polymer Solutions”, Macromolecules, 47 (19), 6919–6924 (2014) Indermeet Kohli, Sharmine Alam, Bhavdeep Patel and Ashis Mukhopadhyay, “Interaction and Diffusion of Gold Nanoparticles in Bovine Serum Albumin Solutions”, Applied Physics Letters, 102 (20), 203705 (2013) Presentations: Sharmine Alam, Indermeet Kohli and Ashis Mukhopadhyay “Dynamics of Nanoparticles in Semidilute Solution of Spheres/Polymers”, 2015 Condensed Matter and Biophysics Seminar, Wayne State University, Detroit, Michigan (USA) Sharmine Alam, Indermeet Kohli and Ashis Mukhopadhyay, “Contrasting Nanoparticles Diffusion in Synthetic and Biopolymer Solutions”, 2015 American Physical Society (APS) Annual Meeting, San Antonio, Texas (USA) Sharmine Alam, Christopher Grabowski, Rami Omari and Ashis Mukhopadhyay, “Critical Adsorption and Colloidal Interaction in Binary Liquid Mixtures”, 2015 American Physical Society (APS) Annual Meeting, San Antonio, Texas (USA) 125 Sharmine Alam and Ashis Mukhopadhyay, “Diffusion of Gold Nanorods in Polymer Solutions”, 2014 American Physical Society (APS) Ohio Section Meeting, Youngstown, Ohio (USA) Sharmine Alam, Indermeet Kohli, Bhavdeep Patel and Ashis Mukhopadhyay, “Adsorption of Gold Nanoparticles from a Crowded Solution on Solid/Liquid Interface”, 2012 American Physical Society (APS) Ohio Section Meeting, Detroit, Michigan (USA) ... 6.5 Supporting Information 100 Chapter – Dynamics of Nanospheres in Biopolymer Solutions 104 7.1 Interaction and Diffusion of Gold Nanoparticles in Bovine Serum Albumin ... 4.5 Supporting Information 66 Chapter - Dynamics of Anisotropic Particles in Biopolymer Solutions 68 5.1 Conjugation of Gold Nanorods with Bovine Serum Albumin Protein ... translational and rotational diffusion of anisotropic nanoparticles in semidilute and entangled polymer solutions Chapter covers the conjugation and interaction of gold nanorods in protein solutions and